Hydrolysis of phosphate esters with polymer-supported catalysts containing cyclodextrin pendant group

  • Cho-Chun Hu
  • Wei-Hsi Chen
  • Chuen-Ying Liu
  • Jen-Luan Chen


Polymer-supported catalysts of several kinds, includingβ-cyclodextrin (P-CD),β-cyclodextrin-diethylenetriamine (P-CD-DETA), andβ-cyclodextrin-N-methylhydroxamate (P-CD-NMHA)-containing polymers, as well as their corresponding metal complexes, were synthesized and examined as catalysts for the hydrolysis of phosphate esters. The kinetic measurements were performed in a phosphate buffer (0.05 M, pH 8.2) at a temperature of 25.0±0.1 °C. Each kinetic run was initiated on introducing ester stock solution (0.13 ml) containing diphenylp-nitrophenyl phosphate (DPPNPP) in dioxane (0.010 M). The rate of hydrolysis of DPPNPP was evaluated by measuring the absorbance of liberatedp-nitrophenol at 402 nm. The dissociation constants between DPPNPP and the polymers P-CD, P-CD-DETA and P-CD-NMHA obtained from Eadie-type plots were 16.8, 16.4 and 8.0 (×10−3 M) and the acceleration factors were 1.5, 2.8 and 8.6 respectively. Hence P-CD-NMHA is the most promising catalyst. The activation parameters, preexponential factor (A) and activation energy using P-CD-NMHA as catalyst, areA=1.2×109 min−1 andEa=43 kJ/mol respectively; the latter was about 12 kJ/mol lower than the activation energy of spontaneous hydrolysis. The results indicate that the catalytic power of P-CD-NMHA may reflect the combined behavior of molecular recognition and nucleophilicity.

Key words

Hydrolysis phosphate esters polymer supported catalyst cyclodextrin pendant group 


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Copyright information

© Kluwer Academic Publishers 1996

Authors and Affiliations

  • Cho-Chun Hu
    • 1
  • Wei-Hsi Chen
    • 1
  • Chuen-Ying Liu
    • 1
  • Jen-Luan Chen
    • 2
  1. 1.Department of ChemistryNational Taiwan UniversityTaipeiTaiwan, ROC.
  2. 2.Chung-Shan Institute of Science and TechnologyTaoyuanTaiwan, ROC.

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